JPH09194880A - Granular nonionic detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a granular nonionic detergent composition having excellent flowabililty under high temperature and high humidity conditions and high antiredeposition effect by mixing a nonionic surfactant with a specified polyalkylene glycol. SOLUTION: This composition comprises a nonionic surfactant, desirably being a fatty acid methyl ester ethoxylate prepared by allowing polyoxyethylenealkyl (or alkenyl) ether and/or fatty acid methyl ester each of which has a melting point of 40 deg.C or below and an HLB of 9-16 to enter into an addition reaction with ethylene oxide and a polyalkylene glycol having a weight-average molecular weight of 30,000-150,000, desirably 40,000-120,000, more desirably 40,000-100,000. The surfactant is desirably used in an amount of 15-50wt.% based on the composition. The polyalkylene glycol is desirably used in an amount of 0.01-5wt.%, based on the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a granular nonionic detergent composition containing a nonionic surfactant as a main component, which has good fluidity of detergent particles under high temperature and high humidity and has a high anti-soil redeposition effect.

[0002]

2. Description of the Related Art Nonionic surfactants generally have a low foaming property, their detergency is hardly affected by the hardness of water, and they are particularly excellent in dirt dispersibility and dirt dispersibility at low temperatures. Further, the nonionic surfactant is an excellent surfactant having good biodegradability, low environmental load, low toxicity and high safety. However, nonionic surfactants are generally liquid at room temperature, and there is a concern that the nonionic surfactant exudes from the granular nonionic detergent product into the detergent container. When the nonionic surfactant seeps into the detergent container, it deteriorates the appearance of the product and the amount of the nonionic surfactant in the contact area of the container decreases, so the cleaning power decreases, and the fluidity of the detergent particles and anti-caking properties are reduced. There were problems such as having a negative effect on sex. By the way, in JP-A-4-339898, 5 to 20% of an amorphous oil-absorbing carrier and a weight average molecular weight of 40 are used.
By blending polyethylene glycol of 0 to 20000, the nonionic surfactant is prevented from exuding. However, the nonionic surfactant itself remains liquid at room temperature, especially at 30 ° C. In the summer when the temperature exceeds the limit, the nonionic surfactant oozes out to deteriorate the fluidity of the detergent particles, which has been a problem.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a granular nonionic detergent composition containing a nonionic surfactant as a main component, which is excellent in fluidity of detergent particles under high temperature and high humidity. And

[0004]

Means for Solving the Problems As a result of extensive studies on the above problems, the present inventor has found that nonionic surfactants can be used in combination with polyethylene glycol having a weight average molecular weight of 30,000 to 150,000 under high temperature and high humidity conditions. It has been found that the flowability of detergent particles can be improved. Therefore, the present invention relates to a granular nonionic detergent composition containing a nonionic surfactant as a main component, which has good fluidity of detergent particles under high temperature and high humidity and has a high anti-soil redeposition effect.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the present invention, various nonionic surfactants can be used as the nonionic surfactant. Examples of preferable nonionic surfactants include:
The following can be mentioned. (1) C3-C22, preferably C8-C18 aliphatic alcohol with C2-C4 alkylene oxide on average 3
Polyoxyalkylene alkyl (or alkenyl) ether added to ３０30 mol, preferably 7-20 mol. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. (2) polyoxyethylene alkyl (or alkenyl)
Phenyl ether. (3) A fatty acid alkyl ester alkoxylate represented by the following formula in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester. R ¹ CO (OA) _n OR ² (R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 3 represents an addition unit of alkylene oxide, n represents the average number of moles of alkylene oxide added, and generally 3 to 3
It is a number of 0, preferably 7 to 20. R ² has 1 carbon atom
Represents a lower alkyl group optionally having 3 to 3 substituents. (4) Polyoxyethylene sorbitan fatty acid ester. (5) Polyoxyethylene sorbite fatty acid ester. (6) Polyoxyethylene fatty acid esters. (7) Polyoxyethylene hydrogenated castor oil. (8) Glycerin fatty acid ester.

Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ethers having a melting point of 40 ° C. or less and an HLB of 9 to 16 and fatty acid methyl ester ethoxylates obtained by adding ethylene oxide to fatty acid methyl ester are particularly preferable. Used for. Further, these nonionic surfactants may be used as a mixture.

The nonionic surfactant is contained in the granular nonionic detergent composition in an amount of preferably 15 to 50% by weight, more preferably 15 to 40% by weight, and particularly preferably 15 to 35% by weight. If this amount is less than 15% by weight, not only the concentration of nonionic surfactant in the resulting detergent particles is low but also the bulk density is low, so that a good detergent effect cannot be obtained unless the amount of detergent used is increased. This is not desirable because it results in a conflict with the downsizing of. It is also not preferable in terms of resource saving. On the other hand, if it exceeds 50% by weight, it is difficult to suppress the exudation, which is not preferable. The polyalkylene glycol used in the present invention has a weight average molecular weight of 30,000 to 150,000, preferably 40,000 to 120,000, and more preferably 40,000 to 100,000. The alkylene group in the polyalkylene glycol includes an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, such as ethylene group and propylene group. Further, the alkylene group may be a mixture of different alkylene groups such as ethylene group and propylene group. When the weight average molecular weight of the polyalkylene glycol is less than 30,000, the effect of improving the fluidity of the detergent particles under high temperature and high humidity is small, while when it exceeds 150,000, the nonionic surfactant and the polyalkylene glycol are The viscosity of the mixed solution of becomes extremely high, which makes it difficult to transfer and measure.

Examples of preferred polyalkylene glycols include: (1) Polyethylene glycol of the general formula HO (CH ₂ CH ₂ O) _n H (n is, for example, 690 to 3400, preferably 910 to 2720) (2) General formula HO (CH ₃ CHCH ₂ O) _n H polypropylene glycol (n is, for example, 520 to 258
0, preferably 690 to 2060. ) (3) General formula HO (CH ₂ CH ₂ O) _n (CH ₃ CHC
H ₂ O) _m H polyethylene polypropylene glycol (n is, for example, 650 to 3230, preferably 860
Is ˜2580, and m is, for example, 24 to 2090, preferably 37 to 1410. )) The form of addition of the polyalkylene glycol is not particularly limited, but it is preferably used by being premixed with a nonionic surfactant. In this case, it may be a by-product in the process of synthesizing the nonionic surfactant, or may be added later to the nonionic surfactant containing no polyalkylene glycol.

It is well known that low molecular weight polyalkylene glycols, for example, low molecular weight polyethylene glycols having a weight average molecular weight of 200 to 2000 are generally excellent in the anti-soil redeposition effect on polyesters. Polyethylene glycol was added in the form of being sprayed on the produced detergent particles. However, in the present invention, rather than using a high molecular weight polyalkylene glycol and spraying the detergent particles,
It was found that the anti-soil redeposition effect can be further improved by premixing and adding the nonionic surfactant.

The polyalkylene glycol is preferably contained in the granular nonionic detergent composition in an amount of 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, and particularly preferably 0.1 to 1% by weight.
It is contained by weight%. If this amount is less than 0.01% by weight,
It is not sufficient to improve the fluidity of the obtained detergent particles, while if it exceeds 5% by weight, the viscosity of the mixed solution of the nonionic surfactant and the polyalkylene glycol becomes high, which is difficult to handle, which is not preferable. . Into the granular nonionic detergent composition of the present invention, the following components which are usually incorporated in detergent raw materials can be incorporated. Various methods can be applied to the method of blending these components. For example, these components may be blended in the granulation treatment step, or may be mixed with the detergent particles obtained by the granulation treatment. . (1) As an inorganic cleaning builder, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium aluminosilicate, sodium tripolyphosphate, sodium pyrophosphate and the like. (2) As organic washing builders, citrate, succinate, polyacrylate, polyacrylic acid-maleic acid copolymer, EDTA and the like. (3) Bis (triazinylamino) stilbene disulfonic acid derivatives, bis (sulfostyryl) biphenyl salts [Tinopearl CBS], etc. as fluorescent agents. (4) As the enzyme, lipase, protease, cellulase, amylase and the like. (5) As a bleaching agent, percarbonate, perborate and the like. (6) Cationic surfactants such as dialkyl-type quaternary ammonium salts as antistatic agents. (7) As surface modifiers, finely divided calcium carbonate, finely divided zeolite, bentonite, and the like. (8) As the anionic surfactant, α-sulfo fatty acid methyl ester salt, linear alkylbenzene sulfonate,
α-olefin sulfonate, alkyl sulfate, fatty acid soap and the like. (9) Cellulose derivatives such as carboxymethyl cellulose as a redeposition preventing agent. (10) As a bulking agent, sodium sulfate, potassium sulfate, sodium chloride and the like. (11) As a reducing agent, sodium sulfite, potassium sulfite and the like.

Next, as a preferred method for producing the granular nonionic detergent composition of the present invention, there are the following methods.

The granular nonionic detergent composition of the present invention comprises a kneading extruder, preferably a kneader, and a mixed solution of a nonionic surfactant and a high molecular weight polyalkylene glycol, and optionally other optional ingredients. Introduce and mix while applying shearing force in a kneader to form a granulation product (solid detergent), then crush granulation by a crushing granulator, preferably a cutter mill or Fitz mill, and compaction It can be manufactured by processing. The granular nonionic detergent composition of the present invention can also be produced by a stirring granulation method. In the stirring granulation method, as a stirring granulator, an internal stirring type granulator such as a high speed mixer, a Shugi mixer, and a Loedige mixer, a mixed solution of a nonionic surfactant and a high-molecular polyethylene glycol, and further The granular nonionic detergent composition of the present invention can be produced by introducing a component that can be optionally added and performing a granulation treatment. In addition, you may spray and add a polyalkylene glycol to detergent particles. Furthermore, the detergent particles thus produced may be coated with a coating agent in a rolling drum, for example.

Further, the detergent particles produced in this way may be post-added with enzymes, perfumes and the like. The obtained granular nonionic detergent composition of the present invention has an average particle size of 3
00-3000 μm, preferably 350-2000 μm
m, particularly preferably 400 to 1000 μm, and the bulk density is 0.5 to 1.2 g / ml, preferably 0.6 to 1.1 g / ml,
Particularly preferably, it is 0.65-1.0 g / ml.

[0014]

The present invention will be described below in more detail with reference to examples and comparative examples. In the examples and comparative examples, each sample was evaluated by the following test methods. [Fluidity test] Detergent particles are allowed to stand for 5 hours in a constant temperature and constant humidity of 40 ° C and 85% RH, and then their fluidity is measured according to JIS Z25.
The angle of repose was measured by the drainage method based on No. 02. [Recontamination Prevention Test] In a two-tub type washing machine (CW-225 manufactured by Mitsubishi Electric) containing 20 ° C. and 30 L of water (3 ° DH),
20 pieces of each of white cotton cloth, acrylic cloth, nylon cloth, 20 g of detergent and 1 g of artificial dirt having the following composition were put therein, washed for 10 minutes, and the anti-soil redeposition effect was visually evaluated according to the following criteria. . ◎: The cloth is not dirty at all ○: The cloth is slightly slightly dirty △: The cloth is slightly dirty ×: The cloth is slightly dirty <Dirt component> Oleic acid 28.3% Triolein 15.6% Cholesterol oleate 12.2% Liquid paraffin 2.5% Squalene 2.5% Cholesterol 2.5% Gelatin 7.0% Inorganic dirt 29.8% Carbon black 0.5% [bulk density] JIS Z2504 The bulk density was measured according to. [Viscosity of Nonionic Solution] The viscosity was measured at 40 ° C. using a BH type viscometer (upper limit value 50 poise).

[Production Example] Examples 1, 4 to 7 and Comparative Examples 1 to 3 Polyethylene glycol (PEG) was mixed with nonionic surfactants in the amounts shown in Tables 1 and 2 below at 50 ° C.
Nonionic liquid was used. This nonionic liquid and other optional components were put into a continuous kneader (KRC-2 type manufactured by Kurimoto Iron Works Co., Ltd.) and kneaded at 40 ° C. for 1 minute to produce a solid detergent. This solid detergent, together with A-type zeolite as a grinding aid, was fitted with Fitzmill (Hosokawa Micron Co., Ltd., DKAS).
O6 type) and pulverized at 15 ° C. for 5 seconds until the average particle diameter became 500 μm. Finally, type A zeolite was added in a rolling drum to coat the obtained detergent particles, and other optional ingredients such as enzymes and fragrances were further added to the granular nonionic detergent composition having the properties shown in Tables 1 and 2. (Average particle size 500 μm) was obtained. Examples 2 to 3 and 8 to 9 As a granulating apparatus, a Reedige mixer (M-20 type manufactured by Matsubo Co., Ltd.) was used, and polyethylene glycol (PEG) was contained in this apparatus in the same manner as in Example 1. The nonionic surfactant and other components were added and stirred and granulated at 40 ° C. for 3 minutes to produce a granular nonionic detergent composition having an average particle diameter of 500 μm. Example 10 Polyethylene glycol (PEG) was granulated in the same manner as in Example except that the crushed detergent particles were sprayed later to produce a granular nonionic detergent composition having an average particle diameter of 500 μm. [Raw materials] The nonionic surfactant and polyethylene glycol (PEG) used in the examples and comparative examples are as follows.

Nonionic Surfactant (1) Nonionic Surfactant-1 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₇ H (Nippon Science Co., Ltd.)
Ltd. Konoru polyoxyethylene alkyl ether obtained by averaging 7 moles addition of ethylene oxide to 20P) (2) nonionic surfactant _{-2 C 13 H 27 O (CH} 2 CH 2 O) 15 (CH 3 CHCH
₂ O) ₃ H (Diadol contains ethylene oxide on average 1
5 moles, the average propylene oxide 3 mol adduct and polyoxyethylene polyoxypropylene alkyl ether) (3) a nonionic surfactant _{-3 C 11 H 23 CO (OCH} 2 CH 2) 9 OCH 3 (4) nonionic surfactant -4 Nonionic surfactant-1 with a weight average molecular weight of 40,000
Containing PEG of 0.4% by weight as a by-product (5) Nonionic surfactant-5 Nonionic surfactant-1 with a weight average molecular weight of 60,000
1% by weight of PEG contained as a by-product Polyethylene glycol (PEG) (1) PEG-1 (reference) Weight average molecular weight 25000 (2) PEG-2 Weight average molecular weight 35000 (3) PEG-3 Weight average molecular weight 70,000 (4) PEG-4 weight average molecular weight 110000 (5) PEG-5 weight average molecular weight 140,000 (6) PEG-6 (reference) weight average molecular weight 160000 polyethylene polypropylene glycol (PEPG) PEPG-1 weight average molecular weight 73000 Structural formula: HO (CH ₂ CH ₂ O) ₁₀₀₀ (CH ₃ CHCH
₂ O) ₅₀₀ H

[0017]

Table 1 Table 1 Example composition (% by weight) 1 2 3 4 5 6 7 Nonionic surfactant 1 10 10 20 20 15 2 15 5 5 3 5 10 10 10 4 25 5 5 10 PEG 2 0.5 3 0.01 0.4 4 0.4 1 5 4 PEPG 11 A type zeolite (for granulation) 30 25 20 20 20 20 20 (for coating) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Grinding aid 5 5 5 5 5 5 5 Amorphous silica 1 4 4 4 4 5 6 Soda ash 30 25 25 25 25 20 10 Sodium sulfite 1 1 1 1 1 1 1 1 Layered polysilicate 5 5 5 5 5 5 5 Soap 0.5 0.5 0.5 0.5 0.5 0.5 0.5 AA-MA 5 5 5 5 5 5 5 Silicone 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Fluorescent agent 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Enzyme 1 1 1 1 1 1 1 1 Other minor components Bla * Bla Bla Bla Bla Bla Bla Evaluation results Angle of repose (°) 45 40 35 40 35 35 35 Anti-recontamination effect Cotton △ △ △ ○ ○ ○ ○ Acrylic △ △ ○ ◎ ◎ ◎ ◎ ◎ Nylon △ △ ○ ◎ ◎ ◎ ◎ Bulk density (g / cc) 0.81 0.83 0.88 0.90 0.91 0.93 0.92 Nonionic liquid viscosity (P) 0.5 0.8 1.1 8 20 37 48 ) Bla * means the remaining amount.

[0018]

[Table 2] Table 1 (continued) Example Comparative Example Composition (% by weight) 8 9 10 1 2 3 Nonionic surfactant 1 10 25 15 10 2 8 5 10 3 10 10 10 10 5 5 30 30 PEG 1 (reference ) 0.1 2 0.5 6 (Reference) 0.5 A-type zeolite (for granulation) 20 13 20 20 20 30 (for coating) 2.5 2.5 2.5 2.5 2.5 2.5 Grinding aid 5 5 5 5 5 5 Amorphous silica 6 8 4 4 6 1 Soda ash 13 10 25 25 14 30 Sodium sulfite 1 1 1 1 1 1 Layered polysilicate 5 5 5 5 5 5 Soap 0.5 0.5 0.5 0.5 0.5 0.5 AA-MA 2 2 5 5 5 5 Silicone 0.1 0.1 0.1 0.1 0.1 0.1 Fluorescent agent 0.2 0.2 0.2 0.2 0.2 0.2 Enzyme 1 1 1 1 1 1 Other minor components Bla * Bla Bla Bla Bla Bla Evaluation result Angle of repose (°) 35 35 45 55 35 70 Anti-recontamination effect Cotton ○ ○ △ △ ○ × Acrylic ◎ ◎ ○ ○ ◎ △ Nylon ◎ ◎ ○ ○ ◎ △ Bulk density (g / cc) 0.90 0.90 0.90 0.88 0.92 0.90 Nonionic liquid viscosity (P) 7 7 0.3 0.6 68 0.3 Note) Bla * means the remaining amount .

The contents of the optional components used in Tables 1 and 2 are as follows. (1) Amorphous silica (Nipseal NS-K manufactured by Nihon Silica Co., Ltd.) (2) A-type zeolite: crystalline sodium aluminosilicate (Shilton B, manufactured by Mizusawa Chemical Co., Ltd.) (3) Grinding aid: crystals Quality Sodium Aluminosilicate (Made by Mizusawa Chemical Co., Ltd., Shilton B) (4) Soda Ash: Light Ash (Made by Asahi Glass Co., Ltd.) (5) Sodium Sulfite: Sodium Sulfite (Shinshu Chemical Co., Ltd.)
(6) Layered polysilicate: SKS-6 (Hoechst Japan) (7) Soap: 1/1 mixture of sodium laurate and sodium oleate (Lion Oleochemical Co., Ltd.)
(8) AA-MA: 7/3 copolymer of acrylic acid and maleic acid, average molecular weight 50,000 (9) PEG: polyethylene glycol (Lion Chemical Co., Ltd., average molecular weight 6000) (10) Silicone: dimethyl Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) (11) Fluorescent agent: 2: 4,4'-bis (2-sulfostyryl) biphenyl disodium (Ciba Geigy Co., Ltd.)
(Tinopearl CBS-X) (12) Enzyme: lipase / protease / cellulase =
1/1/1 Mixture The contents of the optional ingredients used in Tables 1 and 2 above are as follows. (1) Amorphous silica (Nipseal NS-K manufactured by Nihon Silica Co., Ltd.) (2) A-type zeolite: crystalline sodium aluminosilicate (Shilton B, manufactured by Mizusawa Chemical Co., Ltd.) (3) Grinding aid: crystals Quality sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd., Shilton B) Soda ash: Light ash (manufactured by Asahi Glass Co., Ltd.) (4) Sodium sulfite: Sodium sulfite (Kanshu Chemical Co., Ltd.)
(5) Layered polysilicate: SKS-6 (Hoechst Japan) (6) Soap: 1/1 mixture of sodium laurate and sodium oleate (Lion Oleochemical Co., Ltd.)
(7) AA-MA: 7/3 copolymer of acrylic acid and maleic acid, average molecular weight 50,000 (8) Silicone: dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) (9) Fluorescent agent: 2: 4 , 4'-bis (2-sulfostyryl) biphenyl disodium (manufactured by Ciba Geigy Co., Ltd.,
(Tinopearl CBS-X) (10) Enzyme: lipase / protease / cellulase =
1/1/1 mixture

[0020]

According to the present invention, by blending a nonionic surfactant with a polyalkylene glycol having a specific high molecular weight, the fluidity of detergent particles under high temperature and high humidity can be improved and recontamination can be prevented. The effect is also enhanced.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Seiji Abe 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (1)

[Claims] 1. A granular nonionic detergent composition comprising a nonionic surfactant and a polyalkylene glycol having a weight average molecular weight of 30,000 to 150,000.